Dithio amino alkanes



United States Patent 3,444,186 DITHIO AMINO ALKANES Michihiko Sakai and Masayuki Kato, Kyoto, Hikoichi Hagiwara, Osaka, and Kazuo Konishi, Kyoto, Japan, gssignors to Talreda Chemical Industries, Ltd., Osaka,

a an No l rawing. Original application June 25, 1962, Ser. No.

205,088, now Patent No. 3,318,936, dated May 9, 1967.

Divided and this application Sept. 22, 1966, Ser. No.

Claims priority, application Japan, June 27, 1961, 36/ 23,009 int. Cl. C07d; C07c; A0111 9/12 U.S. CI. 260--327 6 Claims This application is a division of our application Ser. No. 205,088, filed June 25, 1962 and now U.S. Patent No. 3,3 18,936.

This invention relates to novel compounds and specified use thereof. More particularly, the instant invention is concerned with the new and useful compounds having in their molecule a tertiary amino group and two substituted thio groups, and with the utilization thereof as pesticides for e.g. agricultural and sanitary purposes.

The objective compounds provided by the present invention are represented by any of the Formulas Ia, Ib and la;

(CHzh-A CH H-CH: CH2CH-CH2(CH:)n-A

i R R,

and

(Ia) (lb) wherein n is an integer from O to 4, A stands for a tertiary amino group, and R stands for two hydrogen atoms, two univalent S-substituting groups or a bivalent S-substituting group.

To make the disclosure simplified, the terms S-substituting group and substituted thio group will be frequently used in this specification for expressing the atomic group combining or to be combined to the sulphur atom or atoms illustrated in the Formulas l and the thio group substituted with the said S-substituting group-i.e. S( R) respectively.

More concretely to say, S-substituting group is, for example, cyano, amidino, an N-monosubstituted amidino group, a lower hydrocarbon residue, at lower carboxylic acid acyl group, a lower sulfonic acid acyl group, a lower sulfinic acid acyl group, an N,N-diloweralkyl-thiocarbamoyl group, an N,N-diloweralkylcarbamoyl group, an 0,0-diloweralkylphosphono group, an 0,0'-diloweralkylthiophosphono group, a loweralkoxy-carbonyl group, a loweralkoxy-thiocarbonyl group, thiocyanato or a mercapto group substituted with a lower hydrocarbon residue as the univalent groups, or, for example, carbonyl, thiocarbonyl, a methylene group substituted with a lower bydrocarbon residue or the bivalent group represented by the part except R of the formula selected from the Formulas I as the bivalent group.

It was further found by the present inventors that these novel compounds illustrated by the Formulas I have a remarkable activity for killing insects, mites and nematodes, and therefore are useful for new-type pesticides.

The principal object of the instant invention is, therefore, to provide a series of novel compounds represented by the Formulas I and their salts, which are useful for killing harmful animals such as insects, mites and nematodes.

Further object is to provide pesticidal compositions which can desirably be applied for agricultural and sanitary purposes to combat against harmful insects including mites and nematodes, the compositions being characterized by containing one or more kinds of the compounds represented by the Formulas I including those in the form of acid salts.

These objective compounds can generally be prepared through any of the following courses.

(A) The substituted thio groups are introduced into the corresponding dihalogeno compounds. For this process, dihalogeno compounds represented by one of the Formulas 11a, 11b and wherein n and A are the same meanings as in the Formulas I, and each of X and X represents a halogen atom, e.g. chlorine, bromine and iodine; can be used and one of the starting compounds represented by the Formulas II is allowed to react with a reactant to replace the halogen atom attached to hydrocarbon skeleton with a mercapto group or with the substituted thio group. As such a reactant, for example, hydrogen sulfide or its salt (such as sodium sulfide, potassium sulfide, ammonium sulfide or a chemical equivalent thereof) to replace the halogen atoms with mercapto groups; thiocyanic acid or its salt (such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate or a chemical equivalent thereof) to replace the halogen atoms with thiocyanato groups (-SCH); a mercaptan (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, hexyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, thiophenol or chemical equivalent thereof) or a mercaptide thereof (such as the sodium mercaptide, the potassium mercaptide, the zinc mercaptide, the silver mercaptide or a chemical equivalent thereof of the mercap tans as exemplified above) to replace the halogen atoms with two mercapto groups both substituted with a lower hydrocarbon residue; thiourea or an N-substituted thiourea (such as methyl thiourea, ethyl thiourea, propyl thiourea, allyl thiourea, butyl thiourea, benzyl thiourea, phenyl thiourea or a chemical equivalent thereof) or an acid salt thereof (such as the hydrochloride, the hydrobromide or a chemical equivalent thereof of thiourea or of the N-monosubstituted thiourea as exemplified above) to replace the halogen atoms with amidinothio or N-monosubstituted amidinothio groups; a lower thiolcarboxylic acid (such as thiolacetic acid, thiolpropionic acid, thiolbenzoic acid, thiolfuroic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt, the lead salt or a chemical equivalent thereof of the thiolcarboxylic acids as exemplified above) to replace the halogen atoms with lower carboxylic acyl-thio groups; a lower thiolsulfonic acid (such as methane thiolsulfonic acid, ethane thiosulfonic acid, propane thiolsulfonic acid, benzene thiolsulfonic acid, p-toluene thiolsulfonic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the thiolsulfonie acids as exemplified above) to replace the halogen atoms with lower sulfonic acid acyl-thio groups; a lower thiolsulfinic acid (such as methane thiolsulfinic acid, ethane thiolsulfinic acid, propane thiolsulfinic acid, benzene thiolsulfinic acid, p-toluene thiolsulfinic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the thiolsulfinic acids as exemplified above) to replace the halogen atoms with lower sulfinic acid acyl-thio groups; an N,N-disubstituted dithiocarbamic acid, such as N,N-diethyldithiocarbamic acid, N,N-dipropyldithiocarbamic acid, N,N-dibutyldithiocarbamic acid, N,N-dipentyldithiocarbamic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the N,N-disubstituted dithiocarbamic acids as exemplified above) to replace the halogen atoms with the N,N-diloweralkyl-thiocarbamoylthio groups; an N,N-disubstituted thiolcarbamic acid (such as N,N-dimethylthiolcarbamic acid, N,N-diethylthiolcarbamic acid, N,N-dipropylthiolcarbamic acid, N,N dibutylthiolcarbamic acid, N,N dipentylthiolcarbamic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the N,N-disubstituted thiolcarbamic acids as exemplified above) to replace the halogen atoms with the N,N-diloweralkyl-carbamoylthio groups; an 0,0'-disubstituted thiolphosphoric acid (such as 0,0-dimethyl hydrogen thiolphosphate, 0,0-diethyl hydrogen thiolphosphate, O-methyl-O'-ethyl hydrogen thiolphosphate, 0,0'-dipropyl hydrogen thiolphosphate, 0,0'-dibutyl hydrogen thiolphosphate, 0,0'-dipentyl, hydrogen thiolphosphate or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the 0,0'-disubstituted thiolphosphoric acid as exemplified above) to replace the halogen atoms with the 0,0'-diloweralkylphosphonothio groups; an 0,0'-disubstituted thiolthionphosphoric acid (such as 0,0-dimethyl hydrogen thiolthionphosphate, 0,0'-diethyl hydrogen thiolthionphosphate, O-methyl-O'-ethyl hydrogen thiolthionphosphate, 0,0- dipropyl hydrogen thiolthionphosphate, 0,0'-dibutyl hydrogen thiolthionphosphate, 0,0'-dipentyl hydrogen thiolthionphosphate or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt or a chemical equivalent thereof of the 0,0-disubstituted thiolthionphosphoric acid as exemplified above) to replace the halogen atoms with the 0,0'-diloweralkyl-thiophosphonothio groups; a xanthogenic acid (such as methyl xanthogenic acid, ethyl xanthogenic acid, propyl xanthogenic acid, pentyl xanthogenic acid or a chemical equivalent thereof) or a salt thereof (such as the sodium salt, the potassium salt, the ammonium salt or a chemical equivalent thereof of the xanthogenic acid as exemplified above) to replace the halogen atoms with the loweralkoxy-thiocarbonylthio groups; a salt (such as the sodium salt, the potassium salt or the ammonium salt) of an O-monoloweralkylester (such as the methyl, the ethyl or the propyl ester) of monothiolcarbonic acid to replace the halogen atoms with the loWeralkoxy-carbonylthio groups; a salt of thiosulfuric acid (such as sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate) to replace the halogen atoms with sulfothio groups in the form of partial salts-Le. in the form of Buntes salts; an alkali metal trithiocarbonate to replace the halogen atoms with a group -SCSS; and hydrogen disulfide or its salt (such as sodium disulfide, potassium disulfide or ammonium disulfide) to replace the halogen atoms with dithio groups between two molecules of the starting halogeno compoundsthereby the l,2,6,7- tetrathiocane ring or the 1,2,5,6-tetrathiocane ring is formedcan be used.

The reaction is carried out by allowing the dihalogeno compound of any of the Formulas II to react with the 4 thiol compound or its functional derivative as mentioned above. Usually there is used the thiol compound or its functional derivative in an amount of not less than twice as much as the used dihalogeno compound on molar basis. When the thiol compound or its functional equivalent in about equimolar amount relative to the dihalogeno compound is used, the corresponding monosubstituted-thio monohalogeno compound is produced as a principal product, on which a similar reaction for replacing the residual halogen atom with the same or the other substituted thio group or a mercapto group is repeatedly brought about; this means is conveniently applied for producing those objective products whose two substituted thio groups are different to each other.

The reaction is preferably carried out in an appropriate solvent such as water, methanol, ethanol, propanol, acetone, methyl ethyl ketone, cyclohexanone, ether, dioxane, tetrahydrofuran, dimethylformamide, pyridine, Z-methyl-S-ethylpyridine, benzene, chloroform or a mixture of two or more kinds of them; the solvent should be selected in accordance with the kind of the used thiol compounds. Usually, the reaction can smoothly proceed at room temperature and, if desired or if required, the reaction mixture may, of course, be heated or cooled according to the progress of the reaction.

(B) The tertiary amino group represented by A in the afore-presented Formulas I is introduced into the corresponding halogeno compounds represented by one of Formulas IIIa, HIb and IIIc:

and

C Hz-C Hr-(llH-(cHi) n X wherein n and R represent the same meaning as in the Formulas I, and X represents a halogen atom, e.g. chlorine, bromine and iodine. The starting halogen compound [represented by one of the Formulas III is allowed to react with a secondary amino, or with a primary amine, and, in the latter case, followed by a further procedure of substitution of hydrogen atom in the resulting secondary amine with a halogenated hydrocarbon or with a ketone or an aldehyde and formic acid according to the so-called Leuckart Reduction (or Reaotion). However, the reaction with a secondary amine is more advantageous than the reaction with a primary amine, since not only there is no need to carry out the subsequent reaction in [the case of the former reaction, but also there is less opportunity to produce a mixture of secondary amine and tertiary amine than in the case of the latter reaction. As the secondary amine to be used for the former reaction, for example, dimethylamine, diethyl' amine, methyl ethylamine, dipropylamine, dibuty-lamine, diamylamine, di-soc-butylamine, di-iso-butylamine, dicyclohexylamine, diphenylamine, monomethylan-iline, monoethylaniline, monomethyltoluidine, pyrrol, pyrrolines, pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine, azirane (ethylenimine) or a chemical equivalent thereof can be used.

The reaction is carried out by allowing the halogeno compound of the Formulas III to react with the aforementioned amine in an excess of the amine or in an appropriate organic solvent such as methanol, ethanol, propanol, acetone, dioxane, dimethylformamide, tetrahydrofuran, benzene, toluene or a chemical equivalent thereof. As one mole of hydrogen halide is produced as the react-ion proceeds, further one mole of the used amine may be consumed for neutralizing the produced hydrogen halide, if any other suitable alkali co-exists in the reaction mixture. Therefore, if it is desired to avoid the consumption of the used amine for the neutralization, e.g. from the point of economical view, the procedure may be somewhat modified into such a manner that a strong alkali is gradually added to the reaction mixture containing the starting halogeno compound and about equivalent of the amine. In general the reaction can be promoted by heating at a temperature lower than 200 C. Of course, according to the kind of the used starting materials, there are cases in which the reaction can be carried out smoothly at room temperature. Moreover, the reaction may be carried out under atmospheric pressure or under superatmospheric pressure if desired, but usually it is suflicient with pressure lower than 30 atmospheres.

When the substituted thio group is thiol group substituted with a lower hydrocarbon residue, another modified procedure can be applied for the production of the objective compound. In this procedure, however, an oxo compound is used as the starting compound instead of the halogeno compound, and the reaction is carried out under reducing conditions. The reducing conditions can be provided by allowing a reducing agent to exist in the reaction mixture or by subjecting the reaction mixture to catalytic reduction. As the reducing agent, for example, an alkali metal and a lower alcohol, iron and hydrochloric acid, iron and acetic acid, sodium amalgam, or a chemical equivalent thereof can be used.

(C) A product, which was produced by either procedure mentioned in item (A) or (B), can be changed into other compounds, also represented by the Formulas I, by modifying the substituted thio groups into some other substituted thio groups. The means for the modification are exemplified as follows:

(a) Among the compounds of the Formulas 1, those having two thiol groups as the substituted thio groups are changed into those having two SS-R' groups, wherein R represents a lower hydrocarbon residue. One of the dithiol compounds is allowed to react with an agent for introducing SR' group, into the thiol groups. As the agent for introducing SR group, a variety of thiol esters can be used. For example, a thiol ester (such as methyl, ethyl, phenyl, benzyl or tolyl ester) of thiosulfuric acid or its water soluble salt (B-untes salts), a thiol ester of a thiolsulfonic acid (such as a methanethiolsulfonate, an ethanethiolsulfonate, a benzenethiolsulfonate, a toluenethiolsulfonate or a chemical equivalent thereof), a thiol ester of a thiolsulfinic acid (such as a methanethiolsulfinate, an ethanethiolsulfinate, a benzenethiolsulfinate, toluenethiolsulfinate or a chemical equivalent thereof), an ester of thiothiocyanate, a sulfenyl halide (such as a sulfenyl chloride, a sulfenyl bromide or a sulfenyl iodide) or any of their chemical equivalents may be used. The hydrocarbon residue of the above-exemplified thiol esters, the residue being to be introduced into the objective compounds together with the sulphur atom to which the residue is combined, may respectively be methyl, ethyl, propyl, isopropyl, allyl, butyl, isobutyl, amyl, hexyl, heptyl, phenyl, tolyl, cyclohexyl, benzyl or their chemical equivalent group, for example.

The reaction is generally carried out in a suitable solvent such as water, methanol, ethanol, dioxane, tetrahydrofuran, dimethylformarnide, benzene, toluene, or a mixture of two or more kinds of them, and smoothly proceeds in the medium adjusted to about pH 7.0 to 9.0 at room temperature. But, in some cases, favorable result may be obtained by heating the reaction mixture at a temperature lower than about 100 C.

(b) The compounds of the Formulas I, which have two thiol groups as the substituted thio groups, are also changed into those having any of carboxylic acyl groups, sulfonic acyl groups, sulfinic acyl groups, a carbonyl group or a thiocarbonyl group as S-substituting groups.

6 One of the dimercapto compounds or mercaptides thereof is allowed to react with an acylating agent.

As the carboxylic acylating agent, for example, a carboxylic acid (such as formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isobutyric acid, methacrylic acid, crotonic acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, sorbic acid, succinic acid, maleic acid, glutaric acid, acetoacetic acid, levulinic acid, chloroacet-ic acid, trichloroacetic acid, cyanoacetic acid, cycloperrtanecarboxylic acid, hexahydrobenzoic acid, benzoic acid, chlorobenzoic acid, nitrobenzoic acid, furoic acid or a chemical equivalent thereof), its acid halide (such as an acid chloride, an acid bromide or an acid iodide of the carboxylic acid as exemplified above), its acid anhydride (including a homogeneous acid anhydride between two molecules of the same carboxylic acid as exemplified above; a mixed (heterogeneous) acid anhydride between the carboxylic acid as exemplified above and the other carboxylic acid as exemplified above; a mixed acid anhydride between the carboxylic acid as exemplified above and a volat-ile acid such as carbonic acid mono ester, or an intramolecular acid anhydride when a carbon chain consisting of two or more carbon atoms is interposed be tween two carboxylic groups), the thiolcarboxylic acid corresponding to the carboxylic acid as exemplified above; the ketone corresponding to the carboxylic acid as exemplified above when the carboxylic acid has the partial structure CH -CH COOH; a lower alkyl ester of the carboxylic acid or of thiolcarboxylic acid as exemplified above (such as the methyl, the ethyl, or the propyl ester of the carboxylic acid or of the thiol carboxylic acid) or a chemical equivalent thereof may be used.

As the sulfonic acylating agent, for example, a sulfonic acid (such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, hexanesulfonic acid, benzenesulfonic acid, o-toluenesulfon-ic acid, p-toluenesulfonic acid, cyclohexanesulfonic acid, phenylmethanesulfonic acid or a chemical equivalent thereof); its acid halide (such as an acid chloride, an acid bromide or an acid iodide of the sulfonic acid as exemplified above) or its acid amide can be used.

As the sulfinic acylating agent, for example, any of sulfinic acids or their acid halides corresponding to the sulfonic acids or their acid halides as mentioned in the preceding paragraph can be used.

For introducing carbonyl or thiocarbonyl group as S- substituting groups, a carbonyl or thiocarbonyl halide (such as phosgene, carbonyl bromide, thiophosgene or thiocarbonylbromide) can be used.

The reaction is generally carried out in a suitable solvent such as water, methanol, ethanol, propanol, dioxane, tetrahydrofuran, pyridine, dimethylformamide, a chemical equivalent thereof or a mixture of two or more kinds of them, and usually proceeds in an alkaline to neutral medium. Usually, the reaction can be carried out at room temperature, but it may be operated under cooling or heating when required.

In a similar way, the compounds of the Formulas I, which have methylene or a methylene: group substituted with a lower hydrocarbon residue as the S-substituting groups, are produced by subjecting the dimercapto compounds or their mercaptides to a condensation reaction with an aldehyde (such as formaldehyde, acetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, caproaldehyde, benzaldehyde, p-tolualdehyde, or =o-tolualdehyde) or a alkylidene halide (such as methylene chloride, methylene bromide, ethylidene chloride, propylidene bromide, benzal chloride or a chemical equivalent thereof). By the reaction, 1,3-dithiolane ring or 1,3-dithiano ring is formed.

(c) The compounds of the Formulas I, which have two lower hydrocarbon residues or a methylene substituted with a lower hydrocarbon residue as S-substituting groups,

are changed into those having two thiol groups as the substituted thio groups, i.e. having hydrogen atoms in place of the S-substituting groups.

The reaction is carried out under reducing conditions and/or in the presence of a heavy metal salt. For the purpose to eliminate the hydrocarbon residue attached to the sulphur atom, fairly strong reduction is required and there is used a rather strong reducing agent such as an alkali metal (e.g. metallic sodium, metallic potassium, metallic lithium), the alkali metal as exemplified above and a lower alcohol (e.g. methanol, ethanol or a chemical equivalent thereof), the alkali metal as exemplified above and an acid (e.g. acetic acid or a chemical equivalent thereof), an amalgam of the alkali metal as exemplified above, an alkali metal amide (e.g. sodium amide, lithium amide or potassium amide), formic acid, or hydrogen in the presence of a metallic catalyst (e.g. Raney nickel, platinium, paradium or a chemical equivalent thereof). The reaction is usually carried out in a suitable solvent such as methanol, ethanol, liquid ammonia, dimethylamine, diethylamine, pyridine, -ethyl-2-methylpyridine, dimethylformamide, diethylether, tetrahydrolfuran, 'dioxane or a chemical equivalent thereof, selected suitably in accordance with the kind of the reducing agent to be used.

In place of or together with the reducing agent, a heavy metal salt can be used for the reaction to eliminate the hydrocarbon residue of the substituted thio group to form the dithiol compounds, which are produced in the form of the mercaptide of the used heavy metal and the subsequent introduction of hydrogen sulfide into the suspension of the mercaptide alfords the free thiol compounds, As the heavy metal salt for this purpose, for example, Water-soluble salt of a metal such as lead, mercury or zinc can be used and the reaction is carried out in a suitable solvent such as water, chloroform, benzene, ether, their chemical equivalent or two or more kind of them. In this case, heating accelerates desirably the reaction velocity.

By the reaction or reactions mentioned above, there can be produced the desired compounds (I) such as:

1,Z-dimercapto-3-dimethylaminepropane,

l,2-dithiocyanato-3-dimethylaminopropane,

1,2-bis(amidinothio)-3-dimethylaminopropane,

1,2-bis benzylthio -3-dimethylaminopropane,

1,2-bis(benzyldithio)-3-dimethylaminopropane,

1,2-bis(n-propyldithio)-3-dimethylaminopropane,

1,2-bis benzoylthio -3-dimethylaminopropane,

1,2-bis(furoylthio)-3-dimethylarninopropane,

1,2-bis(acetylthio)-3-dimethylaminopropane,

1,2-bis(n-hexylthio)-3-dimethylaminopropane,

1,2 bis(methanesulfonylthio)-3-dimethylaminopropane,

1,2 bis (n-propoxycarbonylthio -3-dimethylaminopro pane,

1,2-bis(di-n-propoxyphosphinothio)-3-dimethylaminopropane,

1,2-bis(n-hexyldithio)-3-dimethylaminopropane,

1,2 bis(4 ethoxycarbonylbutyrylthio) 3 dimethylammopropane,

1,2 bis(methyldithio) 3-(3 dimethylaminopropyl) propane,

1,2-bis (p-toluenesulfonylthio -3-diethylaminopropane,

1,2-bis phenoxycarbonylthio -3-diethylaminopropane,

1,2-bis(benzylsulfinylthio)-3-diethylaminopropane,

1,2 his(methylethylcarbamoylthio) 3 diethylaminopropane,

1,2 bis(3 ethoxycarbonylpropionylthio) 3 diethylaminopropane,

1,2 bis(ethoXy-thiocarbonylthio) 3 diethylaminopropane,

1,2-bis(n-propyldithio)-3-diethylaminopropane,

1,2 bis(amidinothio) 3 methylethylaminopropane dihydrochloride,

1,2-bis(benzylthio)-3-methylethylaminopropane,

1,2-bis(diethylcarbamoylthio)-3-diallylaminopropane,

1,2-bis(benzoylthio)-3-di-n-amylaminopropane,

1,2-bis (benzylthio -3-dibenzylaminopropane,

1,2 his(benzeuesulfinylthio) 3 dibenzylaminopropane,

1,2-bis(n-propyldithio)-3-dibenzylaminopropane,

1,2-bis(phenylthio)-3-phen ylethylaminopropane,

1,2-bis (n-amylthio -3-cycloheXyl-n-propylaminopropane,

1,2-bis dibenzylcarbamoylthio -3-dicyclohexylaminopropane,

1,Z-dimercapto-3-dicyclohexy1aminopropane,

1,2-bis (benzylthio) -3-piperidinopropane,

1,2-bis(benzenesulfinylthio)-3-piperidinopropane,

1,2 bis(di-n-propoxyphosphinothio) 3 piperidinopropane 1,2-bis(benzyldithio)-3-piperidinopropane,

1,Z-dimercapto-3-piperidinopropane,

1,2-bis(ethylthio)-3-pyrrolidinopropane,

1,2-bis (methanesulfonylthio) -3-aziridinylprop ane,

1,2 bis(n-propoxythiocarbonylthio) 3 aziridinylpropane,

1,2 bis(dimethoxyphosphinothioylthio) 3 thiomorpholinopropane,

1,2 bis(amidinothio) 3 morpholinopropane dihydrochloride,

1,2-bis(thiocyanatothio)-3-morpholinopropane,

4-dimethylaminomethyl-Z-phenyl-1,3-dithiolane,

4-piperidinomethyl-1,3-dithiolane-2-thione,

4-diethylaminomethyl-Z-phenyl-1,3-dithiolane,

4-dicyclohexylaminomethyl-1,3-dithiolan-2-one,

S-diethylaminopropane-l ,2-bis (sodium thiolsulfate 1,3-bis(henzylthio)-2-dimethylaminopropane,

1,3-bis(acethylthio)-2-dimethylaminopropane,

1,3 bis(diethoxyphosphinothionylthio) 2 dimethylaminopropane,

1,3 bis(diethoxyphosphinothio) 2 dimethylaminopropane,

1,3-dithiocyanato-Z-dimethylaminopropane,

1,3 bis(ethoxythiocarbonylthio) 2 dimethylaminopropane,

1,3 bis(diethylthiocarbarnoylthio) 2 dimethylaminopropane,

1,3 bis(amidinothio) 2 dimethylaminopropane dihydrochloride,

1,3-bis(ethyldithio)-2-dimethylaminopropane,

1,3-bis thiocyanatothio) -2-dimethylaminopropane,

1,3 bis(benzylsulfonylthio) 2 dimethylaminopropane,

1,3-bis(furoylthio)-2-dimethylaminopropane,

1,3-bis (benzoylthio -2-dimethhylaminopropane,

1,3-bis (n-propyldithio -2-dimethylaminopropane,

1,3-bis(benzoylthio)-2-dimethylaminopropane,

1,3-dimercapto-Z-dimethylaminopropane,

1,3 bis(benzylthio) 2 (4 dimethylaminobutyl) propane,

1,3-bis(benzylthio)-2-diethylaminopropane,

1,3-bis benzylthio -2-piperidinopropane,

1,3 bis(ethoxythiocarbonylthio) 2 diethylaminopropane,

1,3-bis(ethylthio)-2-morpholinopropane,

1,3-bis(ethylthio)-2-piperidinopropane,

l,3-bis(ethylthio)-2-pyrrolidinylpropane,

1,3-bis(methylthio)-2-methylethylaminopropane,

1,3-bis(allylthio)-2-diisopropylaminopropane,

1,3-bis(nbutylthio)-2-dibutylaminopropane,

1,3-bis Z-methylhexylthio) -3-dicyclohexylaminopropane,

1,3-bis(phenylthio)-2-aziridinylpropane,

1,3-bis benzylthio -Z-thiomorpholinopropane,

l,3-bis(ethanesulfinylthio) -2-di-n-amylaminopropane,

1,3-bis(benzonesulfonylthio)-2-diphenylaminopropane,

1,3-bis (ethoxycarbonylthio) -2-phenylmethylaminopropane,

1,3-bis(propionylthio)-2-phenylethylaminopropane,

9 1,3-bis (chloroacetylthio -2-diallylaminopropane, 1,3 -bis p-nitrobenzoylthio) -2-aziridinylpropane, 1,3-bis(benzylsulfinylthio)-2-dimethylaminopropane, 1,3-bis(dimethylcarbamoylthio)-2-pyrrol-l-ylpropane, 1,3-bis(phenylamidinothio)-2-pyrrolin1-ylpropane dihydrobromide, 1,3-bis(dimethoxyphosphinothio)-2-diethylaminopropane, 1,3-bis allyldithio -2-di-sec-butylaminoprop ane, 1,3-bis(cyclopentyldithio)-2-diallylaminopropane, 1,3-bis(phenyldithio)-2-di-n-propylaminopropane, 1,3-dimercapto-2-morpholinopropane, Z-dimethylaminopropane-1,3-bis(sodium thiolsulfate), S-dimethylamino-2-propyl-1,3-dithiane, 5methyl-p-tolylamino-1,3-dithian-2-one, S-piperidino-2-phenyl-1,3-dithiane, S-dimethylamino-1,3-dithiane-2-thione, etc.

The compounds (I) are relatively strong bases owing to the tertiary amino group and, though in some case, the amidine or the N-monosubstituted amidino groups or the carbamino groups, and form stable acid addition salts. These compounds (I) which have thiol groups can form salts with a strong alkali owing to the acid property of the thiol group to form a mercaptide. The compounds (I) can be obtained and utilized in the form of acid addition salts or mercaptides as well as in the free form. The acid which can be used to prepare the acid addition salt is suitably selected from those which produce, when combined with the compounds (I) in the form of free bases, addition salts whose anions do not lessen the pesticidal properties inherent in the free bases. The strong alkali which can be used to prepare the mercaptide is also selected from those which produce, when combined with the thiol compounds among the compounds (I), mercaptides whose cations do not lessen the pesticidal properties inherent to the thiol compounds. Appropriate acid addition salts are, for example, those derived from inorganic acids such as hydrochloric, hydrobromic, hydroiodic, chloric, bromic, iodic, perchloric, perbromic, periodic, sulfuric, nitric, phosphoric and arsenic acids, and from organic acid such as maleic, citric, tartaric, oxalic, benzenesulfonic, toluenesulfonic, ethanesulfonic, picric acids or those derived from alkylhalides such as methyl iodide, ethyl iodide, etc. Appropriate mercaptides are, for example, those derived from strong alkalis such as sodium hydroxide and potassium hydroxide, or those from salts of heavy metals such as lead, copper, zinc or the like.

As briefly stated hereinbefore, the novel compounds thus prepared were found to show the activity for killing lower animals such as insects, mites or nematodes, but not to show so much toxicity for vertebrates including mammals and fowls or for plants. Owing to these characteristic properties, the compounds are used as main components for pesticides, especially for insecticides.

When the compounds are brought into practice as pesticides for agricultrual and sanitary purposes, the compounds are generally processed so as to fit for the purposes to form compositions, for example, wettable powder, solution, emulsifiable solution, dust or aerosol.

For the process to prepare the compositions, a variety of adjuvants may be employed. One or more kinds of the compounds are dissolved or dispersed in an appropriate liquid adjuvant when used as solution, emulsifiable solution or aerosol. As the liquid adjuvant to be used as solvents, for example, water, lower alcohols (such as methanol, ethanol, isopropanol, butanol, glycerol or ethylene glycol), ketones (such as acetone, methyl ethyl ketone, cyclohexanone or cyclopentanone), ethers (such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether), aliphatic hydrocarbons (such as n-hexane, gasoline, kerosene, fuel oil, lubricating oil or machine oil); aromatic hydrocarbons (such as benzene, toluene, xylene, solvent naphtha or methyl naphthalene), essential oils, terpenes, chlori- 10 nated biphenyl or cottonseed oil can be used. The solvent is often used in a mixture of the solvents as exemplified above, since the solvent to be used is desired to be not only excellent in its solubility but also less toxic for plants a or human bodies.

For preparing dust composition of the compounds, there are usually employed dust diluents or carriers. One or more kinds of the compounds are finely pulverized, for example, in a ball mill, edge runner or impact pulverized, and the thus pulverized compounds are admixed with dust diluents or carriers. As the diluents or the carriers, for example, vegetable powder (such as soybean flour, wheat flour, tobacco powder, walnut flour or saw dust), clay (such as kaolin, kaolinite, saponite, vermiculite, beidellite, montmorillonite-bentonite or fullers earth or attapulgite), talc, pyrophyllite, calcium lime, magnesrum lime, diatomaceous earth, silica, hydroxyapatite, calcrum carbonate, dolomite, calcite, calcium sulfate, hydrated alumina, carbon black or sulphur can be used.

Another kind of adjuvant is surface active agent which is used as sticking or developing agent, emulsifier, or solubilizer for improving the effect or the stability of compositions. Among commercially available surface active agents, salts of sulfonated castor oil, salts of alkyl aryl sulfonates or non-ionic surfactants such as polyoxyethylene diaryl ether, polyoxyethylene alkyl aryl ether and polyoxyethylene sorbitan monoacylate (the acyl group having 10 to 18 carbon atoms) are preferably used as emulsifying and solubilizing agents for the composition of the present invention.

The pesticidal compositions of the present invention may contain other pesticides (such as benzenehexachloride(Bl-IC), dichlorodiphenyltrichloroethane (DDT), aldrin, dieldrin, endrin, pyrethrin, rotenone, parathion or the other organic phosporus poisons), acaricidea, nematocides, fungicides, herbicides, attractants or repellents. They may also contain growth hormones, fertilizers, or perfumes, all these additions being considered the adjuvants in the composition of the instant invention.

The compounds (I) or compositions thereof of the present invention were observed to have the effect to kill a wide variety of insects, mites and nematodes, and exterminate those harmful animals s exemplified below or at least lessen remarkably the number of surviving animals: The examples of plant feeding insects etc. are:

Colorado potato beetle (Leptinotarsa decomliugnta),

Lalrge )28-spotted lady beetle (Epilach/za vigintioctomacuata 28-Spotted lady beetle (Epilac/zna spagraa orientalis),

Striped flea beetle (Phyllotreta striolata),

Cucurbit leaf beetle (Aulacophora femomalis, adult),

Grape leaf beetle (Acrothinium gackkwitchii, adult),

Red bean beetle (Callosobruchus chinousis),

German cockroach (Blattela germanica),

Rice leaf beetle (Lema orygene),

House fly (Musca domeslica),

Cabbage sawfiy (Athalia rosae iaponensis, larva),

Rice stem borer (Chilo suppressalis),

Tobacco cutworm (Plodenia lizura),

Rice plant skipper (Pal-para guttata, larva),

Rice green caterpillar (Naranga agnescsus, larva),

Cabbage armyworm (Barathra brassicae, larva) Giant bagworm (Cryptozhelea formosz'cola, larva),

Pea bagworm (Cryptozhelen minuscula, larvae),

Pale cluoded yellow (Colias hyale poliographus, larvae),

Cabbage worm (Pier-is i'apae, larva),

Citrus red mite (Petranychus citri),

Soybean aphid (Aphis glycines),

Turnip aphid (Rlzapalosiphum pseudob rassicae),

Two-spitted mite (T etranychus bimaculatus), etc.

Compositions for direct application to vegetation may contain from 0.1% to 10% or more of the compoundts) (I) by weight. When the composition is designed as a concentrate for preparation of sprays or more dilute dusts,

11 the contents of the compound(s) (I) may vary from to 90% by weight.

The pesticidal activity of the compounds (I) is illustrated with reference to a typical representative of experiments.

Experiment 1 An emulsion of the test compound illustrated in Table 1 was sprayed over the soybean plants infested with soybean aphids (Aphis clycz'nes) or over the kidney bean plants on which two-spotted mites (Tetranychus bimaculatus) are kept, the plants being cultivated on a tum-table. After 48 hours, the number of surviving soybean aphids or two-spotted mites was counted to calculate the survival rate. The emulsions used were prepared by dissolving 10 parts by weight of the test compounds in 100 parts by volume of 50% aqueous ethanol mixture containing parts by volume of sorbitan laurate polyoxyethylene ether (Tween 20), and by diluting the solution with tap water so as to make the concentration of the test compound adjust to 0.2%. The figures in Table 1 are mean values of three to six data obtained by experiments carried out parallelly.

TABLE 1 Survival rates (percent) Experiment 2 The test compounds were dissolved in the tap water containing 0.02% of a sticking agent, so as to make the concentration of the test compound adjust as illustrated in Table 2. As the sticking agent, the composition consisting of 20% of alkyphenol polyethylene glycol ether, 12% of lignin sulfonic acid and 68% of aqueous methanol was added. Young leaves of Chinese cabbage were immersed in the thus prepared test solution for several seconds and the wet leaves were allowed to stand in air until the surface of the leaves dried. The leaves thus treated were placed in the pots of 9 centimeters in diameter and 3 centimeters in height. Test insects, i.e., cabbage worms (Pier-is rapae, larvae) or striped flea beetles (Phyllotreta striolata, adults), were set free on the leaves. After 24 hours, the number of killed insects were respectively counted. Results are shown in Table 2.

TABLE 2 Cabbage worms Striped flea beetles' C oncentration of test compound (percent) Concentration of test compound (percent) Kllled/ used Experiment 3 The test compounds were dissolved in the water containing 0.05% of the sticking agent as used in Experiment 2, so as to make the concentration of the test compound TAB LE 3 Concentra- Average of tion oi test survival rates compound of larvae Test compound (percent) (percent) 1,3-bis(propyldithio)-2-dimethylamino- 0. 025 33. 1 propane hydrogen oxalate. 0.05 30.0 4,9-bis(di1nethylamino)-1,2,6,7-tetra- 0. 025 0. 0 thiecane dihydrogen dioxalate. 0.05 0. 0 Control 0 64. 2

Experiment 4 The test compounds were dissolved in the water containing sorbitan laurate polyoxyethylcne ether in an amount of twice as much as the test compounds. Leaves of radish were immersed in the thus-prepared solution and the wet leaves were allowed to stand in air until the surface of leaves dried. The leaves thus treated were placed in glass pots. Twenty larvae of Daikon leaf beetles (Phaedon brassicae) were set free in each pot. After 48 hours, the number of killed insects was counted to calculate mortality. The figure of mortality in Table 4 is the average value of data obtained by twice trials.

TAB LE 4 Concentration of test Average compound mortality Test compound (percent) (percent) 1,3-bls(propyldithio)-2-dimethylamlnopro- O. 1 81. 3 pane hydrogen oxalate. 0.02 77. 3 1,3-dlmercapto-2-diu1ethylamlnopropane 0. 1 100. 0 hydrogen oxalate. 0. 02 100. 0 1,2-dimercapto-3-dimethylaminopropane 0. 1 100.0 hydrogen oxalate. 0. 02 81. 3 1,3-dlthiocyanaio-2-din1ethylaminopropane 0. 1 95. 2 hydrogen oxalate. 0.02 74. 5 1,3-b1s(ethyldithio)+2-dimethylaminopro- 0. 1 100. 0 pane hydrogen oxalate. 0. 02 100. 0 Control 0 0. 0

Experiment 5 The droplets from 1 ml. of pipetted aqueous solution of the test compounds were dropped into a Petri dish until the droplets covered homogeneously the bottom of the dish. After the droplets were dried by airing gently, red bean beetles (Callz'osobruchus chinensis) were set free in the Petri dish. 24 hours later, the number of killed insects was counted to calculate the lethal concentration so)- TAB LE 5 ltretgral cofigenre 10 Test compound r ircen t i 1,3-bis(propyldithlo)-2-dimethylamlnopropaue hydrogen oxalate 0. 005-0. 01 1,3-dimercapto-Z-dimethylaminopropane hydrogen oxalate". 0. 001 1,3-dimercapt dimethylaminopropane disodium ox e 0. 000625-0. 00125 1,3-b1s(ethoxy-throearbonylthio)-2-dimethylamin propane hydrogen oxalate 0. 05-0. 1 1,3-bis(amidinothio) -2-dimethylamlnopropane hydrogen oxalate dihydrochloride 0. 05-0. 1 1,3-bis(ethyldithio)-2-dimethylamlnopropane hydrogen oxalate 0. 00125-0. 0025 l,3-b is(acetylthio)-2-dlmethylamlnopropane hydrogen oxalate 0. 0025-0. 005

Experiment 6 The test compounds were dissolved in the water containing 0.1% of the same sticking agent as used in Ex- *Ma1athion:0,0 dimethyl S-(1,2 dicarboethoxyethyl) phosphodithioate.

Experiment 7 A field test was carried out against striped flea beetles on 25-30 radish plants planted within the sectional area of 3 meters in length and 0.6 meter in width for each test compound. For this experiment radish plants bearing 10 to 15 leaves were used. The test solution prepared as in Table 7 was sprayed over radish plants at the rate of 13 liters per are. The number of the insects on radish plants was counted before spraying and 5 days after spraying and the survival rate was calculated as shown in Table 7.

TAB LE 7 Number of striped flea beetles per radish plant Concentra- 5 days tion of Before after Survival the test spraysprayrate Test compound compound ing ing (percent) 4,9 bis(dimethylamino)-1,2,6,7- tetrathiecane djhydrogen dioxalate 5/10, 000 10. 5 2. 7 23. 7 5-dirnethylamino-1,3-dithiane- 2-thione hydrogen oxalate"--. 5/10, 000 4. 3 3. 3 76. 7 Control 5. 4 5.0 96. G Control (EN)* 3/10, 000 4. 1. 2 24. 0

*EPNzethyl p-nitrophenylthionobenzene phosphoua-te.

Experiment 8 Test on acute toxicity to mice (F -race) in intraperitoneal injection:

EXPERIMENT 8 Dose Test compound (mg/kg.) Killed] Used 1,2-bis(propyldithio) 2-dimethylaminopropane hydrogen oxalate. 500 3/3 4-dimethylaminomethyl-l,3-dithiolane- 2-thione. 500 3/3 The following examples are set forth presently-preferred illustrative of typical compounds represented by the Formulas I of the invention and of the procedure for their preparation, and will serve to make apparent the compounds embraced by the Formulas I and their preparation respectively. Then, pesticidal compositions fit for the practical purposes are also described by means of showing exemplary compositions. It will be understood, of course, that the invention is not limited to the par ticular details of these examples or exemplary compositions since they are no more than the examples of some 14 preferred embodiments of the invention. In these examples and exemplary compositions, temperatures are uncorrected and shown in contigrade. The abbreviation ml. means milliliter or milliliters, and respective amounts of materials shown by either of part(s) or percent" are on weight basis.

EXAMPLE 1 In 50 ml. of ethanol was neutralized 3.4 grams of 1,3- dichloro 2 dimethylaminopropane hydrochloride with 0.9 gram of potassium hydroxide. The solution was gradually dropped into a mixture of 4.9 grams of sodium benzyl mercaptide and 20 ml. of ethanol with stirring at room temperature. After the addition, the mixture was warmed for a little while to separate out sodium chloride, which was then filtered OH. The filtrate was concentrated under reduced pressure to leave an oily substance, which was extracted with ether. The ethereal solution was washed with water and dried over anhydrous sodium sulfate. An ethereal solution saturated with anhydrous oxalic acid was gradually added to the dried ethereal solution to separate out crystals, which were collected by filtration, decolorized and recrystallized from a mixture of ethanol and ether to give 4.5 grams of 1,3 bis(benzylthio) 2 dimethylaminopropane hydrogen oxalate as colorless crystals melting at 132135 EXAMPLE 2 To a solution of 18.1 grams of 1,2 dichloro 3- piperidinopropane hydrochloride in a mixture of 50 ml. each of ethanol and methanol, there was added a solution of 4.4 grams of potassium hydroxide in 50 ml. ethanol under ice-cooling with stirring, whereupon potassium chloride separated and was filtered off with suction. A mixture prepared from 3.6 grams of metallic sodium, 19.5 grams of benzyl mercaptan and 50 ml. of ethanol was added to the above-obtained filtrate and the mixture was refluxed on water bath with stirring for 2 hours. The sodium chloride separating therein was filtered off with suction and the filtrate was concentrated under reduced pressure to dryness to give oily residue, which was dissolved in ether. The ethereal solution was washed with water and dried. Ether was then evaporated to give 23.1 grams of 1,2 bis(benzylth1'o) 3-piperidinopropane as brown oil.

To a solution of 17.3 grams of 1,2 bis(benzylthio)- 3 piperidinopropane in cubic centimeters of ether was added an ethereal solution of oxalic acid to give 17.5 grams of 1,2 bis(benzylthio) 3 piperidinopropane hydrogen oxalate as white and powdery crystals melting at 126 -1Z9 recrystallized from isopropanol.

EXAMPLE 3 In a mixture of 100 ml. each of ethanol and methanol was dissolved 54.4 grams of 1,2-dichloro-3-diethylaminopropane hydrochloride. A mixture of 14 grams of potassium hydroxide and ml. of ethanol was added to the above-prepared solution under ice-cooling, whereupon potassium chloride separated and was filtered off under suction. A mixture prepared from 11.5 grams of metallic sodium, 62.1 grams of benzyl mercaptan and 100 ml. of ethanol was added to the above-prepared filtrate and the mixture was refluxed on water bath with stirring for 2 hours, whereupon sodium chloride separated and filtered ofi" with suction. The filtrate was concentrated under reduced pressure to dryness and the residue was dissolved in ether. The ethereal solution was washed with water, dried and concentrated to dryness to give 67.3 grams of 1,2- bis(benzylthio)-3-diethylaminopropane as brown oil.

EXAMPLE 4 In 150 ml. of ethanol was neutralized 4.8 grams of 1,3- dichloro-2-dimethylaminopropane hydrochloride with 1.4

grams of potassium hydroxide. To the solution was added gradually 5.2 grams of potassium thiolacetate under agitation at room temperature. After the addition, the mixture was warmed for a little while to separate out poassium chloride, which was then filtered off. The filtrate was concentrated under reduced pressure to leave an oily substance, which was extracted with ether. The ethereal solution was washed with water, dried on anhydrous sodium sulfate and warmed to distilled off the ether to leave an oily substance. The oily residue was dissolved in dry ether and an ethereal solution saturated with anhydrous oxalic acid was added gradually to the ethereal solution to separate out crystals, which were recrystallized from a mixture of ethanol and ether to obtain 1,3- bis(acetylthio)-2-dimethylaminopropane hydrogen oxalate as colorless crystals melting at 91 -94.

EXAMPLE 5 A solution of 12.5 grams of 1,2-dichloro-3-dimethylaminopropane hydrochloride in 100 ml. of ethanol was neutralized with 3.6 grams of potassium hydroxide, whereupon potassium chloride separated and was filtered. To the filtrate was added an ethanolic solution of sodium thiolacetate which had been prepared from 9.9 grams of thiolacetic acid, 3 grams of metallic sodium and 100 m. of ethanol. The mixture was allowed to stand overnight and was refluxed on wtaer bath for 40 minutes, whereupon sodium chloride separated and was filtered off. The filtrate was concentrated under reduced pressure to dryness and the oily residue was dissolved in ether. The ethereal solution was washed with water, and dehydrated. An ethereal solution saturated with anhydrous oxalic acid was added dropwise to the dehydrated ethereal solution to separate crystals, which were collected by filtration to obtain 6 grams of l,2-bis(acetylthio)-3-dimethylaminopropane hydrogen oxalate, which decomposes at about 105 -l15, The crude crystals were recrystallized from methanol to give pale yellow crystals decompositing at 124-l28.

EXAMPLE 6 A solution of 9.6 grams of 1,2-dichloro-3-dimethylaminopropane hydrochloride in 50 ml. of ethanol was neutralized with 2.8 grams of potassium hydroxide, whereupon potassium chloride separated and was filtered 01f. To the filtrate, there Was added a solution of 8.2 grams of sodium trithiocarbonate in 50 ml. of ethanol and the mixture was refluxed on a water bath for one hour. After cooling, sodium chloride separated was filtered off and the filtrate was concentrated under reduced pressure. To the residue, there was added 100 ml. of water and extracted three times with 50 ml. of each of ether. All ethereal extracts were combined and dehydrated, to which a solution of 7.5 grams of anhydrous oxalic acid in 100 ml. of ether was added to separate 8.2 grams of crude 4-dimethylaminomethyl 1,3 dithiolane-Z-thione hydrogen oxalate, which decomposes at about 158-168. The crude crystals were recrystallized from aqueous ethanol to give yellow plates decomposing at 1871 89.

EXAMPLE 7 Eighty grams of gaseous ammonia was dissolved in 1.2 liters of anhydrous methanol under cooling and then hydrogen sulfide was saturated therein. To the solution was added 80 grams of 1,2-dibromo-3-dimethylaminopropane hydrochloride and the mixture was allowed to stand overnight in a sealed vessel at room temperature. Then, the mixture was boiled for 2 days, while introducing hydrogen sulfide therein. Resulting crystals were filtered off and the filtrate was concentrated under reduced pressure to leave an oily residue, which was further distilled to obtain 6.0 grams of 1,Z-dimercapto-3-dimethylaminopropane, boiling at 7178/5 mm. Hg.

EXAMPLE 8 In 50 ml. of anhydrous ethanol, there was neutralized 7.9 grams of l,3-dichloro-2-dimethylaminopropane hydrochloride with 2.2 grams of potassium hydroxide to give the free amine. To the solution was added a solution of 6.1 grams of ammonium thiocyanate in ml. of anhydrous ethanol and the mixture was agitated for 2 days at room temperature. After the resulting precipitate had been filtered oflf, the filtrate was concentrated under reduced pressure to leave an oily substance, which was dissolved in ether. The ethereal solution was washed with water and dried. An anhydrous oxalic acid solution in ether was added to the dried ethereal solution to separate crystals, which were collected and recrystalized from a mixture of ethanol and ether to give 7.4 grams of 1,3- dithiocyanato-Z-dimethylaminopropane hydrogen oxalate, melting at 123-124 with decomposition.

EXAMPLE 9 In 50 ml. of anhydrous ethanol was neutralized 7.9 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride with 2.2 grams of potassium hydroxide to give free amine. The free amine was added to a solution of 12.8 grams of potassium ethylxanthogenate in 150 ml. of anhydrousethanol and the mixture was stirred for 2 days at room temperature. The resulting reaction mixture was treated in a similar manner to the preceding example to give 2.9 grams of 1,3-bis(ethoxythiocarbonylthio)-2- dimethylaminopropane hydrogen oxalate, melting at 1 16 with decomposition.

EXAMPLE 10 In 50 ml. of anhydrous ethanol was neutralized 4.9 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride with 1.4 grams of potassium hydroxide to give the free amine. The free amine was added to a solution of 8.6 grams of sodium N,N-diethyldithiocarbamate in ml. of anhydrous ethanol and the mixture was stirred for 2 days at room temperature. The resulting reaction mixture was treated in a similar manner to the preceding example. The obtained crystals were recrystallized from ethanol togive 2.9 grams of 1,3-bis(N,N-diethylthiocarbamoylthio)-2-dimethylaminopropane hydrogen oxalate, melting at 118120 with decomposition.

EXAMPLE 11 In 50 ml. of anhydrous ethanol was neutralized 7.9 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride with 2.2 grams of potassium hydroxide to give the free amine. The free amine was added to a solution of 6.1 grams of thiourea in 100 ml. of anhydrous ethanol and the mixture was stirred for 2 days at room temperature. The resulting reaction mixture was treated in a similar manner to the preceding example to give 2.8 grams of 1,3- bis(amidinothio)-2-dimethylaminopropane/hydrogen oxalate dihydrochloride, melting at 106108 with decomposition.

EXAMPLE 12 In 100 ml. of 50% aqueous ethanol was neutralized 9.6 grams of l,3-dichloro-2-dimethylaminopropane hydrochloride with 2.0 grams of sodium hydroxide to give the free amine, and 24.8 grams of sodium thiosulfate was added thereto. The mixture was heated for a little while, and concentrated under reduced pressure to leave a pale brown oily substance.

On the other hand, 6.2 grams of ethyl mercaptan was dissolved in 50 ml. of 2-normal aqueous sodium hydroxide solution and the solution was saturated with sodium chloride. The above-obtained oily substance was gradually added to the above-prepared solution. After being kept at room temperature for about 5 to 6 hours, the mixture was extracted twice with ether. The ethereal solutions were combined, washed with water and dried.

An anhydrous oxalic acid solution in ether was added to the dried ethereal solution to separate crystals, which were collected and recrystallized from .a mixture of ethanol and ether to give 2.2 grams of 1,3-bis(ethyldi- EXAMPLE 13 A mixture of 24 grams of sodium sulfide and 32 grams of sulfur powder was warmed on water bath to give a uniform solution colored in red orange, and 375 ml. of water and 15 grams of anhydrous potassium carbonate were added thereto. The mixture was cooled with a freezing mixture. A solution of 15 grams of 1,3-dichloro-2-dimethylaminopropane hydrochloride in 75 ml. of water was gradually dropped into the cooled mixture with stirring, during which the reaction temperature was kept at a temperature from -2 to -3. After the addition, the reaction mixture was allowed to stand at -2 to -3 in a refrigerator for 2 days. Then, at room temperature, 50 ml. of 6-normal aqueous sodium hydroxide solution and 0.25 gram of potassium cyanate were added to the reaction mixture and the resulting mixture was extracted twice with chloroform. The extract was treated in a similar manner to the preceding example to give 4.2 grams of 4,9-bis(dimethylamino)-l,2,6,7-tetrathiocane dihydrogen dioxalate melting at 151154 with decomposition.

EXAMPLE 14 In 50 ml. of anhydrous ethanol was changed 7.9 grams of 1,3-dichloro-Z-dimethylaminopropane hydrochloride into the free base with 2.2 grams of potassium hydroxide. The resulting free amine was added to the solution of sodium 0,0-cliethylphosphorodithioate, which had been prepared from 15.1 grams of 0,0'-diethylphosphorodithioic acid and the sodium alcoholate solution prepared from 1.8 grams of metallic sodium and 100 ml. of ethanol, and the mixture was agitated for 2 days at room temperature. Crystallizing sodium chloride was filtered off and the filtrate was concentrated to leave an oily substance. The residue was dissolved in ether and the ethereal solution was washed with water an dehydrated. To the dried ethereal solution was added %-ethereal solution of anhydrous oxalic acid to crystallize the objective compound, which was filtered and recrystallized from a mixture of ethanol and ether to give 8.6 grams of 1,3-bis(diethoxyphosphinothioylthio -2-dimethylaminopropane hydrogen oxalate, melting at 80-82 with decomposition.

The same procedure as mentioned above was brought about except that 14.5 grams of 0,0'-diethylphosphorothiolic acid was used in place of 15.1 grams of 0,0-diethylphosphorodithiolic acid, whereupon 1,3-bis (diethoxyphosphinothio)-2-dimethylaminopropane hydrogen oxalate was obtained.

EXAMPLE 15 A mixture of 15 grams of 1,3-bis(benzylthio)-2-chloropropane and 45 ml. of 31% solution of dimethylamine in benzene was placed in a pressure vessel and heated at 160 for 16 hours. After cooling, resultant dimethylamine hydrochloride was filtered off and the filtrate was concentrated under reduced pressure to dryness. The residue was dissolved in a small amount of water and extracted with 50 ml. of ether, and the ethereal solution was dried over anhydrous sodium sulfate. To the ethereal extract, an ethereal solution saturated with oxalic acid was added until no more precipitate settled. The precipitates were collected and recrystallized to give 11 grams of 1,3-bis (benzylthio)-2-dimethyla-minopropane hydrogen oxalate, melting at 132135.

EXAMPLE 16 A mixture of 7.5 grams of crude 1,3-dibenzylthio-2- chloropropane and 24 ml. of 33 %-solution of diethylamine in benzene was placed in a pressure vessel and heated at 160 for 14 hours. After cooling, resulting diethylamine hydrochloride was filtered off and the filtrate was concentrated under reduced pressure to dryness. A small amount of water and 20 cubic centimeters of ether were added to the residue and an ethereal solution saturated with oxalic acid was added thereto until no more precipitate arose. The precipitates were collected and recrystallized to give 5.5 grams of 1,3-bis(benzylthio)-2-diethylaminopropane hydrogen oxalate, melting at 142.

EXAMPLE 17 A mixture of 15 grams of 1,3-bis(ethoxythiocarbonylthio)-2-bromopropane and 45 ml. of 33%-soluti0n of diethylamine in benzene Was heated on water bath for 3 hours. After cooling, resultant inorganic salts were removed by filtration and the filtrate was concentrated under reduced pressure to dryness. The residue was dissolved in diluted acetic acid and the solution was extracted with ethyl acetate to remove the impurities soluble the solvent. The aqueous layer was adjusted to pH 9.0 with sodium carbonate and extracted twice with 50 ml. of each of ether. An ethereal solution saturated with oxalic acid was added to the ethereal extracts until no more precipitate settled. The precipitates were collected and recrystallized to give 1.5 grams of l,3-bis(ethoxythiocarbonythio)-2-diethylaminopropane hydrogen oxalate.

EXAMPLE 18 Five grams of 1,3-bis(ethylthio)-2-chloropropane and 20 grams of morpholine were heated in 50 ml. of toluene for 7 hours under reflux. After cooling, resulting crystals were filtered off and the filtrate was concentrated under reduced pressure to dryness. The oily residue was dissolved in ether. The ethereal solution was washed with water and dried. An ethereal solution saturated with oxalic acid was added to the dried ethereal solution until no more precipitate settled. The precipitates were collected and recrystallized from acetone to give 4.7 grams of 1,3-bis(ethylthio)-2-morpholinopropane hydrogen oxalate as colorless crystals melting at 121123.

EXAMPLE 19 Five grams of 1,3-bis(ethylthio)-2-chloropropane and 20 grams of piperidine were heated in 50 ml. of toluene under reflux for 10 hours. After cooling, resultant crystals were filtered off and the filtrate was concentrated under reduced pressure to dryness. The oily residue was dissolved in ether and the ethereal solution was washed with water and dehydrated. An ethereal solution saturated with oxalic acid was added to the dehydrated ethereal solution until no more precipitate settled. The precipitates were collected and recrystallized to give 3.2 grams of 1,3-bis (ethylthio)-2-piperidinopropane hydrogen oxalate, melting at 120124.

EXAMPLE 20 Five grams of 1,3-bis(ethylthio)-2-chloropropane and 20 grams of piperidine were heated in 50 ml. of toluene under reflux for 14 hours. After cooling, resulting crystals were filtered off and the filtrate was treated in the same manner as in the preceding example to obtain 3.5 grams of 1,3-bis(ethylthio)'2-pyrrolidinopropane hydrogen oxalate melting at 110113.

EXAMPLE 21 A mixture of 10 grams of 1,3-bis(benzylthiopropan-2- one, 70 ml. of dimethylformamide and 70 ml. of 85% formic acid was placed in a vessel equipped with the apparatus for dehydration and was heated on oil bath at 180 for 10 hours. The reaction mixture was concentrated under reduced pressure and the residue was extracted with ether. The ethereal extract was extracted with 5% hydrochloric acid to collect amine product. The aqueous layer was alkalified with diluted aqueous solution of sodium hydroxide and extracted with ether. The ethereal solution was washed with water, dried over sodium sulfate and concentrated to dryness to give cr-ude 1,3-bis (benzylthio)-2-dimethylaminopropane, which was dissolved in ether and the solution was shaken together with an aqueous solution of oxalic acid to give 1.5 grams of 19 the corresponding hydrogen oxalate melting at 132- 135.

EXAMPLE 22 Ten grams of 2-phenyl-5-hydroxy-l,3-dithiane was dissolved in a mixture of 45 ml. of benzene and 2 ml. of pyridine. Twenty milliliters of thionyl chloride was added to the solution under ice-cooling with stirring, and the reaction was brought about for 2 hours at room temperature. The reaction mixture was poured into ice-water. The aqueous mixture was extracted with ether. The ethereal solution was dehydrated and concentrated to give 9.5 grams of -2-phenyl-5-chloro-1,3-dithiane.

The compound thus obtained was dissolved in 50 ml. of benzene. The solution was mixed with 20 ml. of 32%- dimethyl formarnide in benzene, and the mixture was heated at 160 for 16 hours in an autoclave. The reaction mixture was concentrated and the concentrate was extracted with ether. An ethereal solution saturated with oxalic acid was added to the ethereal extract to crystallize the objective compound, which was filtered and recrystallized from a mixture of ethanol and ether to give 4.0 grams of Z-phenyI-S-dimethylamino-1,3-dithiane hydrogen oxalate, melting at 141-143 with decomposition.

EXAMPLE 23 Nine and half grams of 2-phenyl-4-hydroxymethyl- 1,3-dithiolane was allowed to react with thionyl chloride in a similar way to the procedure in the preceding example to give 2-phenyl-4-chloromethyl-1,3-dithiolane.

The compound was allowed to react with dimethylamine in benzene at 160 for 16 hours in an autoclave to give 4.0 grams of 2-phenyl-4-dimethylaminomethyl- 1,3-dithiolane, which was recrystallized as the hydrogen oxalate to melt at 132 with decomposition.

EXAMPLE 24 A mixture of 40 ml. of anhydrous ethanol and 80 ml. of liquid ammonia was cooled with Dry Ice. A solution of 4.9 grams of 1,3-bis(benzyl'thio)-2-dimethylaminopropane in 40 ml. of anhydrous ethanol and 1.9 grams of metallic sodium were alternatively added to the cooled mixture under agitation, and agitation was further continued for 30 minutes. Then, ammonia and ethanol were distilled otf and 50 ml. of Water was added to the residue. The aqueous mixture was extracted with ether to remove impurities soluble in ether. The aqueous layer was adjusted to pH 9.0 by the addition of hydrochloric acid and saturated with sodium chloride. A solution of 6 grams of sodium benzylthiolsulfate in 20 ml. of water was dropped into the above-prepared solution under agitation, whereupon an oily substance separated, which was extracted with ether. The ethereal extract was mixed with 25 ml. of 7% aqueous oxalic acid solution; the mixture was vigorously shaken and allowed to stand overnight to obtain 2.1 grams of 1,3-bis(rbenzyldithio)-2-dimethylaminopropane hydrogen oxalate as colorless crystals melting at 115-119.

EXAMPLE 25 1;.3-dimercapto 2 dimethylaminopropane, which had been prepared from 4.9 grams of 1,3-bis(-benzylthio)- Z-dimethyl aminopropane in the same manner as in the preceding example, was dissolved in 50 ml. of water and the aqueous solution was adjusted to pH 9.0 with the addition of hydrochloric acid and saturated with sodium chloride. A solution of 2 grams of sodium propylthiolsulfate in 25 ml. of water was added to the aqueous solution saturated with sodium chloride, whereupon an oily substance separated, which was extracted with 80 ml, of ether. The ethereal extract was mixed with 25 ml. of 7% aqueous oxalic acid solution. The mixture was shaken and allowed to stand overnight to obtain 1.5 grams of 1,3-bis(propyldithio)-2-dimethylaminopropane hydrogen oxalate as colorless crystals melting at 130 -134.

2O EXAMPLE 26 A solution of 3 grams of 1,2-dimercapto-3-dimethylaminopropane in 30 ml. of water was adjusted to pH 9.0 with aqueous sodium hydroxide solution and saturated with sodium chloride. A solution of 6 grams of sodium benzylthiosulfate in ml. of water was added to the solution saturated with sodium chloride under agitation, whereupon an oily substance separated, which was ethereal extracts were combined and mixed with ml. extracted three times with ml. each of ether. The of 7%-aqueous oxalic acid solution. The mixture was shaken and allowed to stand overnight to allow the objective compound to crystallize, which was filtered and recrystallized to obtain 2 grams of 1,2-bis(benzyldithio)- 3-dimethyla-minopropane hydrogen oxalate as colorless crystals melting at 115 EXAMPLE 27 A solution of 3 grams of 1,Z-dimercapto-3-dimethylaminopropane-l, 2-dithiol in 30 ml. of water was adjusted to pH 9.0 with 10%-aqueous sodium hydroxide solution and saturated with sodium chloride. A solution of 20 grams of sodium propylthiolsulfate in 20 ml, of water was added to the solution saturated with sodium chloride, whereupon an oil substance separated, which was extracted three times with 30 ml. each of ether. The ethereal extracts were combined and mixed with 25 ml. of 7%- aqueous oxalic acid solution. The mixture was shaken and allowed to stand overnight to crystallize the objective compound, which was filtered and recrystallized to obtain 1.5 grams of l,2-bis(propyldithio)-3-dimethylaminopropane hydrogen oxalate as colorless crystals melting at 128132.

EXAMPLE 28 A mixture of ml. of anhydrous ethanol and 80 ml. of liquid ammonia was cooled with Dry Ice. A solution of 4.6 grams of 1,3-bis(benzylthi-o)-2-dimethylaminopropane in 40 ml. of anhydrous ethanol and 1.9 grams of metallic sodium were alternatively added to the cooled mixture With stirring to allow the reaction to take place. After the reaction ended, ammonia and ethanol were distilled off. The oily residue was dissolved in ml. of water and the solution was extracted with ether to remove oily substances insoluble in water. The aqueous layer was separated and 6.2 grams of benzyl chloride was dropped into the separated solution under ice-cooling and agitation, After 30 minutes from the end of the addition, oily substance separating was extracted with ml. of ether. The ethereal extract was mixed with 25 ml. of 7%-aqueous solution of oxalic acid. The mixture was shaken and allowed to stand overnight, whereupon the objective compound crystallized, which was filtered and dried to give 2.1 grams of 1,3-bis( benzoylthio)-2- dimethylaminopropane hydrogen oxalate as white leaflet crystals melting at l54-156.

EXAMPLE 29 1,3-dimercapto 2 dimethyl-aminopropane, which had been prepared from 4.6 grams of 1,3-bis(-benzylthio)-2- dimethylaminopropane in the same manner as in the preceding example, was dissolved in 50 ml. of water, and 6.5 grams of furoyl chloride was dropped into the aqueous solution. After 30 minutes from the end of the addition, oi-ly substance separating was extracted with 80 ml. of ether. The ethereal extract was mixed with 25 ml. of 7%-aqueous solution of oxalic acid. The mixture was shaken and allowed to stand overnight, whereupon the objective compound crystallized, which was filtered and dried to give 2.5 grams of 1,3-bis(furoylthio)-2-diunethylaminopropane hydrogen oxalate as white crystals melting at 152-158.

EXAMPLE 30 Into a solution of 2.1 grams of 1,2-dimercapto-3-dimcthylammopropane and 3.2 grams of sodium hydroxide in 50 ml. of water was dropped 6.2 grams of benzoyl chloride under ice-cooling and agitation. After 30 minutes from the end of the addition, oily substance separating was extracted with 80 ml. of ether. The ethereal extract was mixed with 25 ml. of 7 %-aqueous solution of oxalic acid. The mixture was shaken and allowed to stand overnight, whereupon the objective compound crystallized, which was filtered and dried to obtain 2.1 grams of 1,2-bis(benzoylthio)-3-dimethyla-minopropane hydrogen oxalate as white leaflet crystals melting at l54-156.

EXAMPLE 3 1 Into a solution of 2.1 grams of 1,2-dimercapto-3-dimethylarninopropane and 3.2 grams of sodium hydroxide in 50 ml. of water was dropped 6.5 grams of furoyl chloride under ice-cooling and agitation. After 30 minutes from the end of the addition, oily substance separating was extracted with 80 ml. of ether. The ethereal extract was mixed with 25 ml. of 7%-aqueous solution of oxalic acid. The mixture was shaken and allowed to stand overnight, whereupon the objective compound crystallized, which was filtered and dried to give 2.5 grams of 1,2-bis (furoylthio)-3-dimethylaminopropane hydrogen oxalate as white crystals melting at 152158.

EXAMPLE 32 A solution of 2.7 grams of 1,2-dimercapto-3-dimethylaminopropane and 4.2 grams of sodium hydroxide in 70 ml. of water was saturated with sodium chloride, and 8 grams of acetic anhydride was dropped into the aqueous solution under ice-cooling and agitation. Then, being added 80 ml. of ether to, the mixture was agitated for additional 30 minutes. The ether layer was separated, dried and mixed with the ethereal solution saturated with oxalic acid. The mixture was shaken and allowed to stand overnight, whereupon the objective compound crystallized, which was filtered and dried to obtain grams of 1,2-bis(acetylthio) 3 dimethylaminopropane hydrogen oxalate as white powdery crystals melting at 115 1 16 C.

EXAMPLE 33 A mixture of 40 ml. of anhydrous ethanol and 80 ml. of liquid ammonia was cooled with Dry Ice. A solution of 4.9 grams of l,3-bis(benzylthio)-2-dimethylaminopropane in 40 ml. of anhydrous ethanol and 1.9 grams of metallic sodium were alternatively added to the cooled mixture. After the mixture was agitated for 30 minutes, ethanol and ammonia were distilled off to leave 3.6 grams of crude 1,S-dimercapto-Ldimethylaminopropane.

The crude product was dissolved in water. The solution was neutralized with hydrochloric acid, saturated with sodium chloride and extracted several times with ethyl acetate. The ethyl acetate extracts were combined, dehydrated and concentrated under reduced pressure to give 2.3 grams of further purified l,3-dimercapto-2-dimethylaminopropane.

EXAMPLE 34 One gram of 4-dimethylaminomethyl-Z-phenyl-1,3-dithiolane was dissolved in a mixture of 20 ml. of ether and 50 ml. of liquid ammonia. To the solution under agitation was added 0.5 grams of metallic lithium bit by bit, whereupon the reaction mixture turned to deep blue in color. The blue color was disappeared by adding 5 ml. of ethanol to the mixture after the reaction had ended. The solvent was distilled off and the residue was dissolved in ice-water. The solution was extracted with ether. The ether layer was separated from the aqueous layer. The ethereal extract was dehydrated and mixed with an etheral solution of oxalic acid to separate 0.5 grams of crystals, which were recrystallized from ethanol to give 4-dimethylamino-l,Z-dithiolane hydrogen oxalate melting at 169-170 with decomposition.

The aqueous layer separated from the ethereal extract was alk-alified. Benzoyl chloride was added to the alkaline aqueous solution to allow the reaction to take place. The reaction mixture was extracted with ether and the ethereal extract was processed in an ordinary manner to give 0.4 gram of 1,2-bis(benzoylthio)-3-dimethylarninopropane hydrogen oxalate which melts 156 with decomposition.

Instead of the metallic lithium above-used in this eX- arnple, 1 gram of metallic sodium was used to carry out the reaction with the essentially same result as mentioned above.

EXAMPLE 35 One gram of 4-dimethylaminomethyl-2-phenyl-1,3-dithiolane was dissolved in a mixture of 20 ml. of ether and 50 ml. of liquid ammonia. To the solution under agitation, 0.5 gram of metallic lithium was added], whereupon the reaction mixture turned to deep blue in color. After 6 ml. of ethanol was gradually added to the reaction mixture, the solvent was distilled ofl under reduced pressure. The residue was dissolved in water and the solution was extracted with ether. An ethereal solution of oxalic acid was added to the ethereal extract separated from the aqueous layer to give 0.4 gram of 4-dimethylamino-1,2-dithiolane hydrogen oxalate, melting at 169 with decomposition.

Benzoyl chloride was added to the alkaline aqueous layer separated from the ethereal extract and the reaction mixture was treated in the same way as in the preceding example to obtain 0.3 gram of 1,2-bis(benzoylthio)-3-dimethylaminopropane hydrogen oxalate, melting at 156 with decomposition.

EXAMPLE 36 To a solution of 2.7 grams of Z-phenyl-S-dimethylamino-1,3-dithiane hydrogen oxalate dissolved in ml. of water was added an aqueous solution of mercuric chloride. The mixture was warmed on water bath for 10 minutes, whereupon benzaldehyde was produced and a mercaptide precipitated. The precipitate was filtered to obtain 4 grams of crude mercaptide melting l00109 with decomposition. The crude mercaptide was suspended in 100 ml. of water and hydrogen sulfide was introduced into the suspension. After filtration, the filtrate was adjusted to pH 8.0 and extracted with ether. The ethereal extract was dehydrated and mixed with an ethereal solution of oxalic acid to obtain 1.8 grams of 1,3-dimercapto-2-dimethylaminopropane hydrogen oxalate melting at with decomposition.

EXAMPLE 37 1,3-dichloro-Z-dimethylaminopropane hydrochloride in an amount of 9.6 grams was allowed to react with 24.8 grams of sodium thiosulfate in water to give an aqueous solution of the disodium salt of l,3-bis(sulfothio)-2-dimethylaminopropane. The aqueous solution was dropped into an aqueous solution of 7.5 grams of disodium salt of l,3-dimercapto-Z-dimethylaminopropane, which had been saturated with sodium chloride and thoroughly cooled with ice-water. The resulting reaction mixture was extracted with ether. The ethereal extract was washed with water and dried. As anhydrous ethereal solution of oxalic acid was added to the dried ethereal solution to separate crystals, which were filtered and recrystallized from a mixture of ethanol and ether to give 4.2 grams of 4,6-bis(dimethylamino)-1,2,6,7-tetrathiecane dihydrogen dioxalate as pale yellow leaflets melting at l54156 with decomposition.

EXAMPLE 3 8 Into a solution of 1,3-dimercapto-7-dimethylaminoheptane in methanol the solution was prepared by adding 2.5 grams of sodium boron hydride into a solution of 5.1 grams of 3-dimethylaminobutyl-1,2-dithiolane in 50 ml. of methanol and by allowing the mixture to stand for 20 minutes, there was added 17 grams of benzyl chloride, and the mixture was stirred for five minutes at room temperature and for further one hour on water bath. The reaction mixture was concentrated to leave an oily substance, which was extracted with ether. The ethereal solution was washed with water and dried over anhydrous sodium sulfate. An ethereal solution of anhydrous oxalic acid was added to the dried ethereal solution to separate yellow oil. The yellow oil was collected, mixed with 20%- aqueous potassium solution and extracted with ether. The ethereal solution was washed with water, dried and concentrated to give 1.3 grams of 1,3-bis(benzylthio)-7-dimethylaminoheptane as an undistilizable oil.

Composition 1 One part of 1,3-bis(benzylthio)-2-diethylaminopropane was adsorbed on 1.5 parts of diatomaceous earth and admixed with 1.5 parts of silicic acid (white carbon). The mixture Was diluted with 96 parts of talc to prepare 1%- dust composition to be used for fruit trees.

Composition 2 In 30 parts of methyl ethyl ketone was dissolved parts of 1,3-dithiocyanato-2-dimethylaminopropane, and to the solution was added a solution of parts of a surfactant (which mainly consists of 70% of polyoxyethylenealkylphenylethers and of sodium arylsulfonates under the trade name Newk-algen 1515) in parts of toluene to prepare 5%-emulsifiable solution to be used for rice plants.

Composition 3 Forty-five parts of finely pulverized 1,3-dimercapto-2- dimethylaminopropane hydrogen oxalate was mixed with 5 parts of silicic acid (the aqueous suspension of which is neutral), and to the mixture were added 48 parts of the fine-grained clay for the use of paper making and 2 parts of sodium ligninsulfonate. The mixture was finely pulverized and admixed to prepare 45%-Wettable powder to be used for vegetables.

Composition 4 A solution of 5 parts of abietic acid polyglycol ester in 10 parts of acetone was adsorbed on 35 parts of finely pulverized 1,2 dimercapto-3-dimethylaminopropane hydrogen oxalate and the mixture was dried in air at a temperature lower than To the dried mixture were added 58 parts of finely grained clay and 2 parts of sodium ligninsulfonate and the mixture was thoroughly pulverized and admixed to prepare 35 %-wettable powder to be used for fruit trees.

Composition 5 One part of 1,3 -bis(ethylthio)-2-morpholinopropane was adsorbed on a mixture of 1 part of bentonite and 1.3 parts of diatomaceous earth and the mixture was granulated in a granulator. 0n the other hand, 10 parts of lactose was wetted with a small amount of starch paste and dried also to form granules. Both granules prepared as above and 1 part of talc were admixed and the mixture was punched to prepare 7%-tablets of 15 millimeters in diameter, which are used as nomatocide.

Composition 6 Composition 7 In 50 parts of ethylene glycol monomethyl ether was dissolved 15 parts of 1,3-bis(dimethoxyphosphinothioylthio)-2-dimethylaminopropane hydrogen oxalate. Into the solution were added and dissolved 20 parts of a surfactant (which mainly consists of 70% of polyoxyethylene alkylphenylethers and 30% of organic sulfonates under the trade name Sorpol 2283T) and 15 parts of xylene, to prepare l5%-emulsifiable solution to be used for fruit trees.

Composition 8 One and half parts of l,3-bis(amidinothio)-2-dimethylaminopropane hydrogen oxalate dihydrochloride, 0.5 part of silicic acid and 8 parts of talc were admixed and finely pulverized. The pulverized mixture was diluted with 90 parts of the clay, whose apparent specific gravity was about 0.5-0.6, to prepare 1.5%-dust composition to be used for fruit trees.

Composition 9 Fifty parts of 1,2 bis(ethoxythiocarbonylthio) 3 dimethylaminopropane was mixed with 15 parts of benzene, 15 parts of a surfactant (which mainly consists of polyoxyethylenediphenylethers under the trade name Newkalgen 200 5) and 20 parts of another surfactant (which mainly consists of polyoxyethylenealkylphenylethers under the trade name Newkalgen P55) to prepare 50%-emulsifiable solution to be used for fruit trees.

Composition 10 Fifty parts of 1,2-bis(isopropyldithio) 3 dimethylaminopropane hydrogen oxalate was pulverized in a fluid energy mill and was mixed with 50 parts of potassium chloride. The mixture was again pulverized in a disintegrator to prepare 50%-wettable powder to be used for vegetables.

Composition 12 Ten parts of 1,3-bis(benzyldithio)-2-dimethylaminopropane hydrogen oxalate was pulverized. To the pulverized compound were added 2 parts of sodium ligninsulfonate, 5 parts of polyoxyethyleneoctylphenylether, 3 parts of silicic acid and parts of clay, and the mixture was thoroughly admixed to prepare 10%-wettable powder.

Composition 13 Forty parts of 1,3-bis(ethylthio)-2-piperidinopropane hydrogen oxalate was pulverized. To the pulverized compound were added 2 parts of sodium ligninsulfonate, 5 parts of polyoxyethylenenonylphenylether, 6 parts of silicic acid and 47 parts of fine-grained clay, and the mixture was thoroughly admixed to prepare 40%-wettable powder.

Composition 14 Two parts of thoroughly pulverized 1,3-bis(ethoxythiocarbonylthio)-2-diethylamino propane hydrogen oxalate was diluted with 98 parts of talc to prepare 2%-dust composition.

Having thus disclosed the invention, what is claimed is:

25 26 4,9-bis(dimethy1amino)-1,2,6,7-tetrathiecane. ROBERT V. HINES, Primary Examiner. 1,3-bis (ethyldithio -2-dimethy1aminopropane.

1,3-bis(benzyldithio)-2-dimethy1amin0propane. U.S. C1. X.R.

. 1,3-bis(nr0 1dithio)-2-dimeth lamino r0 ane.

ILbis(begzyligithio) 3 dimethy1min0prgpa%e 260 239, 243, 247.1, 268, 293.4, 326.3, 326.83, 326.84, Xz bis(n pmpyldithio) 3 dimethylaminopmpane 5 347.2, 429.9, 435, 438.1, 440, 453, 454, 455, 465, 465.5, 501.1, 501.14, 501.15, 501.21, 543, 563, 564, 567.5, 567.6,

References C'ted 134, 141, 145, 186, 187, 190, 202, 208, 209, 211, 245, UNITED STATES PATENTS 246, 248, 250, 267, 274, 275, 277, 285, 286, 289, 293, 5/1967 Sakai 6t a1 260-454 10 294, 298, 300, 301, 302, 303, 316, 326, 325, 329, 330

ash-kph)? 

1. 4,9-BIS(DIMETHYLAMINO)-1,2,6,7-TETRATHIECANE. 